Dyestuffs dyeing on mordant and process of making same



UNITED STATES PATENT OFFICE.

MANFRED ALIOTH AND ERNST BODMER, OF BASE-L, SWITZERLAND, ASSIGNORS TO DURAND & HUGUENIN S. A.., OF BASEL, SWITZERLAND, A CORPORATION OF SWITZERLAND.

DYESTUFFS DYEING ON MOBDANT AND PROCESS OF MAKING SAME.

No Drawing.

To all whom it may concern:

Be itlrnown that we, MANFRED ALIOTH and ERNST BODMER, both citizens of the Swiss Republic, and residents of Basel, Switzerland, have invented new and useful Dyestuffs Dyeing on Mordant and Process of Making Same, of which the following is a full, clear, and exact specification.

We have found that by oxidizing one molecule of methylene-dianilidosalicylic acid resulting'from the action of formaldehyde on anilido-sa1icyclic acid (see Annalen, 210, page 34.2) together with one molecule of salicylic acid, there is obtained a new dyestuff dyeing on mordant.

This dyestufl' is distinguished from the analogous not anilidated already known product (see Berichte der deutschen Chemischen Gresellschaft, vol. 25, page 939), that is to say, the aurinetricarboxylic acid, by its more red tint and it is suitable for dyeing chromed wool.

Concerning its application for printing purposes we have found that it gives dull and little intense tints, but that his sulfoderivative gives, when printed with chromium, far more vivid, more intense and more fast tints than those given by the nonsulfonated body. The sulfo group enters probably the aniline nucleus.

There is "consequently a great advantage to sulfonate the new body and the dyestuif derived therefrom will be an interesting representative of the chromium dyeing dyestuffs either for cotton printing or for dyeing chromed wool.

Obviously the process is not limited to the above defined product. Instead of salicyclic acid there can be employed for instance o-cresotini'c acid, generally any o-oxyca-r-' boxylic acid of the aromatic series. as well for the preparation of a methylene-di-anilido-o-oXyca-rboxylic acid as for the component to be oxidized with this latter methylene derivative.

For the substitution of the carboxylic group there can be employed, instead of aniline, an aniline-derivative containing N0 a halogen, CH etc., as substituent in the nucleus, in other words, any aromatic amine having at least one free amino-group.

Broadly spoken, the 'procm shows the 4 following steps:

1. The anilidation of the o-oxycarboxylic acid.

Patented Jan. 17, 1922.

Serial No. 484,155.

2. The reaction of the formaldehyde on the anilidated product for forming a mothylene derivative of the anilido-o-oxycarboxylic acid.

3. The oxidation of one molecule of methylene dianilido o oxycarboxylic acid together with one molecule of o-oxycarboxylic acid.

4. The sulfonation of the dyestufi'.

Nevertheless the invention is not limited to the succession of steps in the above given order. For instance, the salicylic acid can at first be anilidated and the resulting anilido-salicylic acid be condensed afterwards with formaldehyde, or the salicylic acid can be condensed at first with formaldehyde and the resulting methylene-disalicylic acid be anilidated afterwards, in order to obtain in botgli cases the methylene-dianilido-salicylic aci Shortly the invention relates to the manufacture of dyestuffs corresponding probably to the general formula:

OH COOH ortho wherein R, and R designate each an arcmatic nucleus which may still contain sub- 35 stituents other than those already indicated in the formula and R, an aromatic nucleus, substituted or not, but, if substituted, preferably substituted by a sulfo group.

Example I. 106.5 kg. of anilido-salicylic acid are dissolved at 20 to 25 C. in 700 kg. of sulfuric acid of 66 Baum. To this solution are added. while stirring, at ordinary temperature. 7.5 kg. of paraformaldehyde and the stirring is continued for several hours. Then there are added, while stirring, 34.5 kg. of

salicylic acid and, after dimolution oft-his latter, the mass is oxidized by addition of 30 kg. of sodium nitrite.

This addition is effected by little portions and the temperature is maintained, during the oxidation, at 30 to 50 C. When the oxidation is terminated, the mm is cooled down and poured into ice water. The red dyestuff precipitates, it is filtered off, washed until neutrality with cold water and dried. The yield is to kg. of acid dyestufi.

Solubilized by its mixture with sodium 1 4O the end, the mass is still maintained for 1 1 hour, at 50 to 55 (1., 1t 1s and poured into'ice water.

carbonate, the product can be employed for dyeing chromed wool. F or its sulfonation, the dyestuif isdissolved in a fivefold, quantity of sulfuric acid of 66 B. The red solution thus obtained is heated for 1 to 2 hours at 90 to959- C. until a sample of the mass'dissolves in cold solution of sodiumacetate. The mass is then cooled down and poured into salt water, the dyestuff is separated from the liquid and washed with salt water until neutrality. The dyestui'l is for its most part soluble in water, it becomes entirely soluble addition of a little sodium carbonate. It has the above mentioned properties.

Example [1.

The same dyestuff can be obtained by anilidating the methylene-drsahcyhc acid and oxidizing the'r'eaction product together wlth salicylic acid.

To this purpose, 20 kg. of methylenedisalicylic acid (Berichte der deutschen Chemischen 'Gesellschatt, vol. 31,page 148) are suspended in 100 kg. of benzene and to this suspension areadded 18 kg. of aniline and progressively kg. of phosphorus trichlorine. Themass is boiled until the escapem ent of hydrochloric acid ceases, it is then cooled'down and the solid product separated from' the liquid- The product thus obtained is first washed with dilute hydrowhile heating progressively to 40 C." At

- The red product is separated from the liquid and washed until neutrality. It is identical with the non-sulfonated dyestutf of Example I. 7 7 i Y fIJ (ZI7Z.-]7 Z6 U].

23 kg. of anilido-o-cresotinic acid (Berichte der deutschen Chemischen' (lo-sell- V schaft, vol. -35,ipage"36l5) are dissolved in 1150 kg. of sulfuric acid o'i: 66 Baum. To

the'solutio n thus obtained are added, at low temperature, 1.5 kg. of paralorm'a ldchydc an'd'gthe mass is stirred for several hours at ordinary teimperatu're. Then 7.6 kg. of

o-cr'esotinic' acid are added and after disso' luti'on or" this latter the mass is'oxidized at 30'to 50 C. with 6 kg, of sodium nitrite. in the c'ourse'of 3, to a hours After cooling, themass is poured into ice water.- The separation and the sul fonation are carried outas 'indic atedin Example I. JThere are. 0b.:

then cooled down 7 tained 30 kg. of a deep-red powder giving,

when dyed on chromed wool and when printed on cotton with a chromium mordant,

a red shade more-bluish than that obtained with the dyestuff of Example I.

Example IV.

25 kg. of paranitranilido-salicylic acid (Beilstein II, page V 1500; J ahresberichte fiber-die F ortschritte der Chemie, 1875, page 747) are dissolved at to C. in 150 kg. of sulfuric acid-of 66 Be. and to the solution thus obtained there are added, at low temperature, 1.5 kg. of paraitormaldehyde. The mass is stirred at ordinary temperature for 5 hours and abandoned to itself during a night The next day,there are added 7 kg. of salicylic acid and after dissolution the mass is oxidized at -40 C. with 6 kg. of so-di'umnitrite. At the end, themass is maintained for 2 hours at to (1., then cooled down and poured into ice water. The dyestuif is then separated from the liquid and washed until neutrality It is mixed with sodium carbonate. "lVhen dyed on chromed wool, it gives red tints, somewhat more yellowish than those obtained with the product of Example II. For the preparation of the sulfonated"dyestuti. one proceeds in the same manner asfinExample I.

What we claim is: Y r

1. The herein described process for the manufacture of new red dyestutfsdyeingon mo'rdant, consisting in oxydizing one molecule of an aromatic o-oxycarboxylioacid together' withl one molecule of an aromatic methylene d1aryl1do-o oxycarboxylic acid.

2. The herein describedprocess for the manufacture of new red dyestuflsrdyeing on mordant, consisting in arylidating an aromatic methylene-di-o-oxycarboxylic acid and oxidizing one molecule of the aromatic methylene diarylidoo oxycarboxylic acid thus obtained together with one moleculeof anaromatic o-oxycarboxylic acid. a

The herein described process for the manufacture of new red dyestuffs dyeing on mordant, consisting in arylidating an aromatic o-oxycarboxylic acid, reacting with formaldehyde on'the arylido-o-oxycarboxylie acid {thus obtained and "oxidizing one molecule or the resulting aromatic methylene-diarylido oeoxycarboxylic aci'd together boxyl-ic acid. 2

4. The herein described .pro'cess for the manufacture of new red dyestuffsdyeing on mordant, cons sting'inoxydizmg one molecule of an aromatic o-oxyc'arboxylic acid .together w th" one 'molecule of an aromat1c methylene diarylido o -"oxycarboxylic acid and sulfonating thefdyestulffthus obtained. 5. The herein described process-forthe with one molecule of an aromatic o-oxycarmanufacture offnew red dyestufi's'dyeing on mordant, consisting in arylidating an aromatic methylene-di-o-oxycarboxyhc acid,

oxidizing one molecule of the aroma-tic methylene-diarylido-o-oxycarboxylic acid thus obtained together with one molecule of an aromatic o-oxycarboxylic acid and sulfonating the dyestuff thus obtained.

6. The herein described process for the manufacture of new red dyestuffs dyeing on mordant, consisting in arylidating an aromatic o-oxycarboxylic acid, reacting with formaldehyde on the resulting arylido-o oXyca-rboxylic acid, oxidizing one molecule of the aromatic methylene-diarylido-o-oxycarboxylic acid thus obtained together with one molecule of an aromatic o-oxycarboxylic acid and sulfonating the dyestuflf thus obtained.

7. As new products, the herein described red dyestuffs corresponding to the formula:

oonnm I OHQCOOH ortho wherein R R R stand each for an aromatic nucleus, whlch may be substituted, the

said dyestuffs dyeing chromed wool red tints of good fastness.

8. As new products, the herein described red sulfonated dyestuffs corresponding to the formula:

OH on RzHNOC R -CR CO.NHRg

2 onQcooH ortho wherein R and R stand each for an aromatic nucleus, which may be substituted, whilst R, stands each for an aromatic nucleus substituted by a sulfo group, the said dyestuffs giving, when dyed on chromed wool and when printed on cotton with chromium mordants red vivid tints of good fastness.

In witness whereof we have hereunto signed our names this 24th day of June, 1921, in the presence of two subscribing witnesses.

MANFRED ALIOTH. ERNST BODMER. WVitnesses FRIDK. KUnz, AMAND BAUER. 

